Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes

William R. McNamara, Robert C. Snoeberger, Gonghu Li, James M. Schleicher, Clyde W. Cady, Macarena Poyatos, Charles A. Schmuttenmaer, Robert H. Crabtree, Gary W Brudvig, Victor S. Batista

Research output: Contribution to journalArticle

121 Citations (Scopus)

Abstract

A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering photocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2′:6,2″- terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II) → Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.

Original languageEnglish
Pages (from-to)14329-14338
Number of pages10
JournalJournal of the American Chemical Society
Volume130
Issue number43
DOIs
Publication statusPublished - Oct 29 2008

Fingerprint

Electron injection
Anchors
Nanoparticles
Injections
Photosensitizing Agents
Photosensitizers
Photooxidation
Adsorbates
Time measurement
Ultraviolet spectroscopy
Scaffolds
Transition metals
Metal ions
Paramagnetic resonance
Electrons
Atmospheric humidity
Suspensions
Ligands
Pumps
Thin films

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

McNamara, W. R., Snoeberger, R. C., Li, G., Schleicher, J. M., Cady, C. W., Poyatos, M., ... Batista, V. S. (2008). Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes. Journal of the American Chemical Society, 130(43), 14329-14338. https://doi.org/10.1021/ja805498w

Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes. / McNamara, William R.; Snoeberger, Robert C.; Li, Gonghu; Schleicher, James M.; Cady, Clyde W.; Poyatos, Macarena; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W; Batista, Victor S.

In: Journal of the American Chemical Society, Vol. 130, No. 43, 29.10.2008, p. 14329-14338.

Research output: Contribution to journalArticle

McNamara, WR, Snoeberger, RC, Li, G, Schleicher, JM, Cady, CW, Poyatos, M, Schmuttenmaer, CA, Crabtree, RH, Brudvig, GW & Batista, VS 2008, 'Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes', Journal of the American Chemical Society, vol. 130, no. 43, pp. 14329-14338. https://doi.org/10.1021/ja805498w
McNamara, William R. ; Snoeberger, Robert C. ; Li, Gonghu ; Schleicher, James M. ; Cady, Clyde W. ; Poyatos, Macarena ; Schmuttenmaer, Charles A. ; Crabtree, Robert H. ; Brudvig, Gary W ; Batista, Victor S. / Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 43. pp. 14329-14338.
@article{86a3fa5eb5884baf87ba5c11ffaa3f49,
title = "Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes",
abstract = "A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering photocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2′:6,2″- terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II) → Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.",
author = "McNamara, {William R.} and Snoeberger, {Robert C.} and Gonghu Li and Schleicher, {James M.} and Cady, {Clyde W.} and Macarena Poyatos and Schmuttenmaer, {Charles A.} and Crabtree, {Robert H.} and Brudvig, {Gary W} and Batista, {Victor S.}",
year = "2008",
month = "10",
day = "29",
doi = "10.1021/ja805498w",
language = "English",
volume = "130",
pages = "14329--14338",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "43",

}

TY - JOUR

T1 - Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes

AU - McNamara, William R.

AU - Snoeberger, Robert C.

AU - Li, Gonghu

AU - Schleicher, James M.

AU - Cady, Clyde W.

AU - Poyatos, Macarena

AU - Schmuttenmaer, Charles A.

AU - Crabtree, Robert H.

AU - Brudvig, Gary W

AU - Batista, Victor S.

PY - 2008/10/29

Y1 - 2008/10/29

N2 - A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering photocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2′:6,2″- terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II) → Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.

AB - A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering photocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2′:6,2″- terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II) → Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.

UR - http://www.scopus.com/inward/record.url?scp=54849412280&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=54849412280&partnerID=8YFLogxK

U2 - 10.1021/ja805498w

DO - 10.1021/ja805498w

M3 - Article

VL - 130

SP - 14329

EP - 14338

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 43

ER -